U.S. patent application number 11/177334 was filed with the patent office on 2006-02-02 for cosmetic composition comprising a water-dispersible linear sulphonic polyester and a modified guar gum, methods employing this composition and uses.
Invention is credited to Cecile Bebot, Ludivine Laurent, Sabine Vrignaud.
Application Number | 20060024260 11/177334 |
Document ID | / |
Family ID | 35732456 |
Filed Date | 2006-02-02 |
United States Patent
Application |
20060024260 |
Kind Code |
A1 |
Bebot; Cecile ; et
al. |
February 2, 2006 |
Cosmetic composition comprising a water-dispersible linear
sulphonic polyester and a modified guar gum, methods employing this
composition and uses
Abstract
The present disclosure relates to a cosmetic composition
comprising, in a cosmetically acceptable medium, at least one
water-dispersible linear sulphonic polyester and at least one
modified guar gum, methods employing this composition, and uses
thereof.
Inventors: |
Bebot; Cecile; (Clichy,
FR) ; Laurent; Ludivine; (Clichy, FR) ;
Vrignaud; Sabine; (Clichy, FR) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER;LLP
901 NEW YORK AVENUE, NW
WASHINGTON
DC
20001-4413
US
|
Family ID: |
35732456 |
Appl. No.: |
11/177334 |
Filed: |
July 11, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60620335 |
Oct 21, 2004 |
|
|
|
Current U.S.
Class: |
424/70.11 |
Current CPC
Class: |
A61K 2800/5422 20130101;
A61K 8/737 20130101; A61K 2800/594 20130101; A61K 8/85 20130101;
A61Q 5/06 20130101; A61K 2800/5424 20130101 |
Class at
Publication: |
424/070.11 |
International
Class: |
A61K 8/85 20060101
A61K008/85 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 29, 2004 |
FR |
04 08396 |
Claims
1. A cosmetic composition comprising, in a cosmetically acceptable
medium, at least one water-dispersible linear sulphonic polyester
and at least one modified guar gum.
2. A cosmetic composition according to claim 1, wherein the at
least one water-dispersible linear sulphonic polyester is a
polycondensate of at least one dicarboxylic acid or an ester
thereof, of at least one diol, and of at least one difunctional
sulphoaryldicarboxyl compound substituted on the aromatic ring by
an --SO.sub.3M group wherein M is chosen from a hydrogen atom and a
metal ion.
3. A cosmetic composition according to claim 2, wherein M is a
metal ion chosen from Na.sup.+, Li.sup.+ and K.sup.+.
4. A cosmetic composition according to claim 1, wherein the at
least one water-dispersible linear sulphonic polyester is obtained
from isophthalic acid, sodium salt of sulphoisophthalic acid,
diethylene glycol and 1,4-cyclohexanedimethanol.
5. A cosmetic composition according to claim 1, wherein the Tg of
the at least one water-dispersible linear sulphonic polyester is
greater than or equal to 50.degree. C.
6. A cosmetic composition according to claim 1, wherein the at
least one water-dispersible linear sulphonic polyester is present
in an amount ranging from 0.1 to 40% by weight with respect to the
total weight of the composition.
7. A cosmetic composition according to claim 6, wherein the at
least one water-dispersible linear sulphonic polyester is present
in an amount ranging from 1 to 30% by weight with respect to the
total weight of the composition.
8. A cosmetic composition according to claim 7, wherein the at
least one water-dispersible linear sulphonic polyester is present
in an amount ranging from 5 to 25% by weight with respect to the
total weight of the composition.
9. A cosmetic composition according to claim 1, wherein the at
least one modified guar gum is chosen from at least one guar gum
alkylated by at least one C.sub.1-8 alkyl group, at least one guar
gum hydroxyalkylated by at least one C.sub.1-8 hydroxyalkyl group
and at least one guar gum acylated by at least one C.sub.1-8 alkyl
group.
10. A cosmetic composition according to claim 9, wherein the at
least one modified guar gum is a hydroxypropylated guar gum.
11. A cosmetic composition according to claim 1, wherein the at
least one modified guar gum is present in an amount ranging from
0.05 to 10% by weight with respect to the total weight of the
composition.
12. A cosmetic composition according to claim 11, wherein the at
least one modified guar gum is present in an amount ranging from
0.1 to 5% by weight with respect to the total weight of the
composition.
13. A cosmetic composition according to claim 12, wherein the at
least one modified guar gum is present in an amount ranging from
0.5 to 3% by weight with respect to the total weight of the
composition.
14. A cosmetic composition according to claim 1, wherein the at
least one water-dispersible linear sulphonic polyester and the at
least one modified guar gum are present in a ratio of from 0.01 to
100.
15. A cosmetic composition according to claim 14, wherein the ratio
of the at least one water-dispersible linear sulphonic polyester to
the at least one modified guar gum ranges from 1 to 75.
16. A cosmetic composition according to claim 14, wherein the ratio
of the at least one water-dispersible linear sulphonic polyester to
the at least one modified guar gum ranges from 2 to 50.
17. A cosmetic composition according to claim 1, further comprising
at least one additional fixing polymer chosen from anionic,
cationic, amphoteric and nonionic fixing polymers and mixtures
thereof.
18. A composition according to claim 17, wherein the cationic
fixing polymers are chosen from homopolymers and copolymers of
acrylic and methacrylic esters and amides comprising aminated
functional groups, cationic polysaccharides, quaternary copolymers
of vinylpyrrolidone and of vinylimidazole, and chitosans.
19. A composition according to claim 17, wherein the anionic fixing
polymers are chosen from homopolymers and copolymers of acrylic and
methacrylic acid and their salts, copolymers of crotonic acid,
copolymers of C.sub.4-C.sub.8 monounsaturated carboxylic acids and
anhydrides, polyacrylamides comprising carboxylate groups,
homopolymers and copolymers comprising sulpho groups, anionic
polyurethanes and anionic grafted silicone polymers.
20. A composition according to claim 17, wherein the amphoteric
fixing polymers-are chosen from-copolymers comprising acidic vinyl
units and comprising basic vinyl units, acylated and crosslinked
polyaminoamides, polymers comprising zwitterionic units, polymers
derived from chitosan, modified (C.sub.1-C.sub.5)alkyl vinyl
ether/maleic anhydride copolymers amphoteric polyurethanes and
amphoteric grafted silicone polymers.
21. A composition according to claim 17, wherein the nonionic
fixing polymers are chosen from polyalkyloxazolines, vinyl acetate
homopolymers and copolymers, acrylic ester homopolymers and
copolymers, acrylonitrile copolymers, styrene homopolymers and
copolymers, polyamides, vinyllactam homopolymers other than
vinylpyrrolidone homopolymers, vinyllactam copolymers, nonionic
polyurethanes and nonionic grafted silicone polymers.
22. A cosmetic composition according to claim 17, wherein the at
least one additional fixing polymer is present in an amount ranging
from 0.1 to 20% by weight with respect to the total weight of the
composition.
23. A cosmetic composition according to claim 22, wherein the at
least one additional fixing polymer is present in an amount ranging
from 0.5 to 10% by weight with respect to the total weight of the
composition.
24. A cosmetic composition according to claim 1, further comprising
at least one additional thickening polymer other than the at least
one modified guar gum.
25. A cosmetic composition according to claim 24, wherein the at
least one additional thickening polymer is present in an amount
ranging from 0.01 to 20%.
26. A cosmetic composition according to claim 25, wherein the at
least one additional thickening polymer is present in an amount
ranging from 0.05 to 10% by weight with respect to the total weight
of the composition.
27. A cosmetic composition according to claim 1, further comprising
at least one compound chosen from silicones, silicone-comprising
fatty substances and silicone-free fatty substances.
28. A cosmetic composition according to claim 27, wherein the at
least one compound chosen from silicones, silicone-comprising fatty
substances and silicone-free fatty substances is present in an
amount ranging from 0.01 to 20% by weight relative to the total
weight of the composition.
29. A cosmetic composition according to claim 28, wherein the at
least one compound chosen from silicones, silicone-comprising fatty
substances and silicone-free fatty substances is present in an
amount ranging from 0.05 to 10% by weight relative to the total
weight of the composition.
30. A cosmetic composition according to claim 1, further comprising
at least one additive chosen from nonionic, anionic, cationic and
amphoteric surface-active agents, additional nonionic, anionic,
cationic and amphoteric polymers, ceramides and pseudoceramides,
vitamins and provitamins, water-soluble and fat-soluble sunscreen
agents which may or may not comprise silicone, solid fillers and
particles, pearlescent and opacifying agents, glitter, active
particles, dyes, sequestering agents, plasticizing agents,
solubilizing agents, acidifying agents, basifying agents,
neutralizing agents, inorganic and organic thickening agents,
antioxidants, hydroxy acids, penetrating agents, fragrances and
preservatives.
31. A cosmetic composition according to claim 30, wherein said
solid fillers and particles are chosen from inorganic and organic
pigments which may or may not be colored.
32. A method for shaping, fixing, and/or form retention of a
hairstyle comprising applying to hair a cosmetic composition
comprising, in a cosmetically acceptable medium, at least one
water-dispersible linear sulphonic polyester and at least one
modified guar gum.
33. A method according to claim 32, wherein the at least one
water-dispersible linear sulphonic polyester is obtained from
isophthalic acid, sodium salt of sulphoisophthalic acid, diethylene
glycol and 1,4-cyclohexanedimethanol.
34. A method according to claim 32, wherein the at least one
modified guar gum is a hydroxypropylated guar gum.
35. A method for creating a water-resistant hairstyle, comprising
applying to hair a cosmetic composition comprising, in a
cosmetically acceptable medium, at least one water-dispersible
linear sulphonic polyester and at least one modified guar gum.
Description
[0001] This application claims benefit of U.S. Provisional
Application No.60/620,335, filed Oct. 21, 2004, the contents of
which are incorporated herein by reference. This application also
claims benefit of priority under 35 U.S.C. .sctn. 119 to French
Patent Application No. 04 08396, filed Jul. 29, 2004, the contents
of which are also incorporated by reference.
[0002] The present disclosure relates to a cosmetic composition
comprising, in a cosmetically acceptable medium, at least one
water-dispersible linear sulphonic polyester and at least one
modified guar gum, and the methods employing this composition. The
present disclosure also relates to the use, for fixing the
hairstyle, of a cosmetic composition comprising, in a cosmetically
acceptable medium, at least one water-dispersible linear sulphonic
polyester and at least one modified guar gum.
[0003] Cosmetic compositions for the shaping and/or form retention
of the hairstyle can be in the form of a spray and comprise a
solution, generally alcoholic, and one or more components, referred
to as fixing components, which are generally polymeric resins, the
role of which may be to form connections between the hairs or to
sheath the hairs. These fixing components are often formulated as a
mixture with various cosmetic adjuvants.
[0004] Cosmetic compositions containing fixing components, as
described, are generally packaged either as a pump-action spray or
in an appropriate aerosol container pressurized using a propellant.
The aerosol system comprises, on the one hand, a liquid phase (or
fluid) and, on the other hand, a propellant.
[0005] It is also possible to use such styling compositions in the
form of gels, creams or foams.
[0006] Once applied to the hair, it is intended that the fixing
components in such styling compositions will make it possible to
fix the hair. However, the polymers commonly used as fixing agents
in styling compositions often do not make it possible to retain the
shaping of the hairstyle when the latter is brought into contact
with water for a long period of time, such as, for example, when
brought into contact with rain or perspiration or during bathing:
sea bathing or bathing in a swimming pool, and the like.
[0007] The present inventors have discovered, surprisingly, that
the use of a cosmetic composition comprising, in a cosmetic
acceptable medium, at least one water-dispersible linear sulphonic
polyester and at least one modified guar gum makes it possible to
fix and/or shape hairstyles and/or to retain the shaping of
hairstyles when the latter are brought into contact with water for
a prolonged period of time. Within the meaning of the present
disclosure, this phenomenon is referred to as "resistance to
water".
[0008] The term "prolonged period of time", as used herein, is
understood to mean being brought into contact with water for a
minimum period of time of one minute, such as 10 minutes or, for
example, 20 minutes.
[0009] The compositions disclosed herein also make it possible to
obtain a hairstyle which is resistant to atmospheric moisture.
[0010] The compositions according to the present disclosure make
possible good fixing and/or good form retention of the hair, that
is to say, a styling effect which may last throughout the day,
indeed even for several days, and/or which may exhibit good
resistance to water, such as good resistance to repeated bathing.
These compositions may also exhibit the advantage of being removed
on shampooing. Overall, these compositions make it possible to
confer good cosmetic properties.
[0011] Disclosed herein, therefore, is a cosmetic composition
comprising, in a cosmetically acceptable medium, at least one
water-dispersible linear sulphonic polyester and at least one
modified guar gum.
[0012] Also disclosed is a method for the shaping or form retention
of the hairstyle in which the above-described cosmetic composition
is employed.
[0013] Further disclosed herein is the use of a cosmetic
composition comprising, in a cosmetically acceptable medium, at
least one water-dispersible linear sulphonic polyester and at least
one modified guar gum as a styling composition for the fixing
and/or the form retention of the hair, such as when it is brought
into contact with water for a prolonged period of time, for
instance in the case of rain or perspiration or when bathing: such
as sea bathing or bathing in a swimming pool. According to this
embodiment, the use of the composition makes it possible to obtain
a water-resistant hairstyle (wherein "hairstyle" refers to the
shaping of the hair). Further, in this embodiment, the cosmetic
composition can be provided in a form chosen from lotions, sprays,
foams, gels and creams.
[0014] Other characteristics, aspects and advantages of the present
disclosure will become even more clearly apparent on reading the
description and examples which follow.
[0015] The term "styling cosmetic composition", within the meaning
of the present disclosure, is understood to mean a composition for
the shaping or form retention of a hairstyle.
[0016] The cosmetically acceptable medium used in the compositions
disclosed herein is an aqueous, aqueous/alcoholic or alcoholic
medium optionally comprising at least one additional organic
solvent. The alcohol may be a monohydroxylated alkanol chosen from
lower C.sub.1-C.sub.4 alcohols, such as ethanol, isopropanol,
tert-butanol or n-butanol; in at least one embodiment, the alcohol
used is ethanol.
[0017] The concentration of alcohol in the compositions according
to the present disclosure ranges from 0 to 50%, such as from 0 to
10% or from 0 to 5%, by weight with respect to the total weight of
the composition.
[0018] The additional organic solvents which can be used in the
compositions according to the present disclosure include polyols,
such as propylene glycol, polyol ethers and their mixtures.
[0019] The concentration of additional organic solvent in the
compositions according to the present disclosure ranges from 0 to
30%, such as from 0 to 20%, by weight with respect to the total
weight of the composition.
Water-Dispersible Linear Sulphonic Polyesters
[0020] As stated above, the composition according to the present
disclosure comprises a water-dispersible linear sulphonic
polyester. The term "water-dispersible linear sulphonic polyester"
is understood herein to mean any sulphonic polyester exhibiting an
ability to form a dispersion, that is to say a two-phase system,
where the first phase is formed of finely divided particles
uniformly distributed in the second continuous phase.
[0021] The term "sulphonic polyester" is understood herein to mean
copolyesters obtained by polycondensation of at least one
dicarboxylic acid or of one of its esters, of at least one diol and
of at least one difunctional sulphoaryldicarboxyl compound
substituted on the aromatic ring by an --SO.sub.3M group in which M
is chosen from a hydrogen atom and a metal ion, such as Na.sup.+,
Li.sup.+ or K.sup.+.
[0022] The water-dispersible linear sulphonic polyesters used in
the context of the present disclosure exhibit a weight-average
molecular mass ranging from 1000 to 60,000, such as from 4000 to
20,000, as determined by gel permeation chromatography (or
GPC).
[0023] The glass transition temperature (Tg) of these sulphonic
polyesters may range from 10.degree. C. to 100.degree. C. In at
least one embodiment, the Tg of the at least one water-dispersible
linear sulphonic polyester used is greater than or equal to
50.degree. C. The glass transition temperature (Tg) is measured by
differential scanning calorimetry (DSC) according to Standard ASTM
D3418-97.
[0024] The water-dispersible linear sulphonic polyesters useful
herein are described in more detail, for example, in U.S. Pat. Nos.
3,734,874, 3,779,993, 4,119,680, 4,300,580, 4,973,656, 5,660,816,
5,662,893 and 5,674,479.
[0025] In at least one embodiment, the water-dispersible linear
sulphonic polyesters comprise at least units derived from
isophthalic acid, from a salt of sulphoaryldicarboxylic acid and
from diethylene glycol. For example, the sulphonic polyesters may
be obtained from isophthalic acid, sodium salt of sulphoisophthalic
acid, diethylene glycol and 1,4-cyclohexanedimethanol.
[0026] Mention may be made, as examples of water-dispersible linear
sulphonic polyesters, of those known under the INCI name
Diglycol/CHDM/Isophthalates/SIP and sold under the trade names
"Eastman AQ Polymer" (AQ35S, AQ38S, AQ55S, AQ48 Ultra) by Eastman
Chemical.
[0027] The concentration of water-dispersible linear sulphonic
polyester(s) used in the compositions according to the present
disclosure ranges from 0.1 to 40%, such as from 1 to 30%, or from 5
to 25%, by weight with respect to the total weight of the
composition.
Modified Guar Gums
[0028] The composition according to the invention comprises at
least one modified guar gum.
[0029] The term "modified guar gum", within the meaning of the
present disclosure, is understood to mean -guar gums alkylated by
at least one C.sub.1-8 alkyl group, guar gums hydroxyalkylated by
at least one C.sub.1-8 hydroxyalkyl group or guar gums acylated by
at least one C.sub.1-8 acyl group.
[0030] For example, the modified guar gum may be hydroxypropylated
guar gum, such as that sold under the name Jaguar HP 105 by
Rhodia.
[0031] The concentration of modified guar gum(s) used in the
compositions according to the present disclosure ranges from 0.05
to 10%, such as from 0.1 to 5% or from 0.5 to 3%, by weight with
respect to the total weight of the composition.
[0032] Advantageously, the water-dispersible linear sulphonic
polyester/modified guar gum ratio ranges from 0.01 to 100, such as
from 1 to 75 or from 2 to 50.
[0033] he compositions according to the present disclosure can also
comprise at least one additional cosmetic adjuvant, such as those
mentioned below.
Fixing Polymers
[0034] With respect to fixing polymers as the at least one
additional cosmetic adjuvant, any anionic, cationic, amphoteric or
nonionic fixing polymer, and mixtures thereof, used in the art can
be used in the compositions according to the present
disclosure.
[0035] The additional fixing polymers may be soluble in the
cosmetically acceptable medium or may be insoluble in this same
medium and, in this case, used in the form of dispersions of solid
or liquid polymer particles (e.g., latex or pseudolatex).
Anionic Fixing Polymers
[0036] The anionic fixing polymers that may be useful are polymers
comprising groups derived from carboxylic, sulphonic or phosphoric
acid and have a number-average molecular mass ranging from 500 to
5,000,000.
[0037] The carboxyl groups may be contributed by unsaturated mono-
or dicarboxylic acid monomers such as those corresponding to the
formula: ##STR1##
[0038] in which
[0039] n is an integer from 0 to 10,
[0040] A.sub.1 is a methylene group, optionally connected to the
carbon atom of the unsaturated group, or to the neighboring
methylene group when n is greater than 1, via a heteroatom, such as
oxygen or sulphur,
[0041] R.sub.7 is chosen from a hydrogen atom, a phenyl group, and
a benzyl group,
[0042] R.sub.8 is chosen from a hydrogen atom, a lower alkyl group,
and a carboxyl group, and
[0043] R.sub.9 is chosen from a hydrogen atom, a lower alkyl group,
a --CH.sub.2--COOH group, a phenyl group, and a benzyl group.
[0044] In the abovementioned formula, a "lower alkyl group," means,
in at least one embodiment, a group having 1 to 4 carbon atoms,
such as methyl and ethyl groups.
[0045] In at least one embodiment, the anionic fixing polymers are
chosen from homopolymers or copolymers of acrylic and methacrylic
acid or their salts, copolymers of crotonic acid, copolymers of
C.sub.4-C.sub.8 monounsaturated carboxylic acids or anhydrides,
polyacrylamides comprising carboxylate groups, homopolymers or
copolymers comprising sulpho groups, anionic polyurethanes and
anionic grafted silicone polymers.
[0046] Suitable anionic fixing polymers comprising carboxyl groups
according to the present disclosure may be chosen from, but are not
limited to:
[0047] A) Homo- or copolymers of acrylic or methacrylic acid or
their salts, such as the products sold under the names
Versicol.RTM. E or K by Allied Colloid and Ultrahold.RTM. by BASF,
the copolymers of acrylic acid and of acrylamide sold in the form
of their sodium salts under the names Reten 421, 423 or 425 by
Hercules or the sodium salts of polyhydroxycarboxylic acids.
[0048] B) Copolymers of acrylic or methacrylic acid with a
monoethylenic monomer, such as ethylene, styrene, vinyl esters or
esters of acrylic or methacrylic acid, optionally grafted onto a
polyalkylene glycol, such as polyethylene glycol, and optionally
crosslinked. Such polymers are disclosed, for example, in French
Patent No.1 222 944 and German Application No. 2 330 956, the
copolymers of this type comprising, in their chain, an optionally
N-alkylated and/or -hydroxyalkylated acrylamide unit, such as
disclosed in Luxembourgian Patent Applications Nos. 75370 and 75371
or provided under the name, Quadramer by American Cyanamid. Mention
may also be made of copolymers of acrylic acid and of
C.sub.1-C.sub.4 alkyl methacrylate and terpolymers of
vinylpyrrolidone, of acrylic acid and of C.sub.1-C.sub.20 alkyl
methacrylate, for example lauryl methacrylate, such as that sold by
ISP under the name Acrylidone.RTM. LM, and methacrylic acid/ethyl
acrylate/tert-butyl acrylate terpolymers, such as the product sold
under the name Luvimer.RTM. 100 P by BASF. Mention may also be made
of the methacrylic acid/acrylic acid/ethyl acrylate/methyl
methacrylate copolymers in aqueous dispersion sold under the name
Amerhold.RTM. DR 25 by Amerchol.
[0049] C) Copolymers of crotonic acid, such as those comprising, in
their chain, vinyl acetate or propionate units and optionally other
monomers, such as allyl or methallyl esters, vinyl ethers or vinyl
esters of a linear or branched saturated carboxylic acid comprising
a long hydrocarbon chain, such as those comprising at least 5
carbon atoms, it optionally being possible for these polymers to be
grafted or crosslinked, or alternatively another monomer chosen
from vinyl, allyl and methallyl esters of .alpha.- or .beta.-cyclic
carboxylic acids. Such polymers are disclosed, inter alia, in
French Patents Nos. 1 222 944,1 580 545, 2 265 782, 2 265 781, 1
564 110 and 2 439 798. Commercial products coming within this class
are the Resins 28-29-30, 26-13-14 and 28-13-10 sold by National
Starch.
[0050] D) Copolymers of C.sub.4-C.sub.8 monounsaturated carboxylic
acids or anhydrides chosen from:
[0051] copolymers comprising [0052] (i) at least one acid or
anhydride chosen from maleic, fumaric and itaconic acids or
anhydrides and [0053] (ii) at least one monomer chosen from vinyl
esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, or
acrylic acid and its esters, the anhydride functional groups of
these copolymers optionally being monoesterified or
monoamidated.
[0054] Such polymers are disclosed, for instance, in U.S. Pat. Nos.
2,047,398, 2,723,248 and 2,102,113 and GB Patent No. 839 805.
Commercial products are, for instance, those sold under the names
Gantrez.RTM. AN or ES by ISP;
[0055] copolymers comprising [0056] (i) at least one anhydride unit
chosen from maleic, citraconic and itaconic anhydride units and
[0057] (ii) at least one monomer chosen from allyl or methallyl
esters, optionally comprising at least one group chosen from
acrylamide, methacrylamide, .alpha.-olefin, acrylic or methacrylic
ester, acrylic or methacrylic acid, and vinylpyrrolidone groups in
their chain, the anhydride functional groups of these copolymers
optionally being monoesterified or monoamidated.
[0058] These polymers are, for example, disclosed in French Patents
Nos. 2 350 384 and 2 357 241.
[0059] E) Polyacrylamides comprising carboxylate groups.
[0060] The homopolymers and copolymers comprising sulpho groups
(i.e., derived from sulphonic acid) are, for example, polymers
comprising vinylsulphonic, styrenesulphonic, naphthalenesulphonic
or acrylamidealkylsulphonic units.
[0061] These polymers can be chosen from:
[0062] salts of polyvinylsulphonic acid having a molecular mass
ranging from 1,000 to 100,000, as well as copolymers with an
unsaturated comonomer, such as acrylic or methacrylic acids and
their esters, as well as acrylamide or its derivatives, vinyl
ethers and vinylpyrrolidone;
[0063] salts of polystyrenesulphonic acid, such as the sodium salts
sold, for example, under the name Flexan.RTM. 500 and Flexan.RTM.
130 by National Starch. These compounds are disclosed, for
instance, in French Patent FR 2 198 719;
[0064] salts of polyacrylamidosulphonic acids, such as those
mentioned in U.S. Pat. No. 4,128,631, for example, the
polyacrylamidoethylpropanesulphonic acid sold under the name
Cosmedia Polymer HSP 1180 by Henkel.
[0065] Mention may be made of the anionic branched block polymer
sold under the name Fixate G-100 by Noveon, as other anionic fixing
polymers which can be used according to the present disclosure.
[0066] According to the present disclosure, the anionic fixing
polymers may, in at least one embodiment, be chosen from acrylic
acid copolymers, such as the acrylic acid/ethyl
acrylate/N-tert-butylacrylamide terpolymers sold in particular
under the name Ultrahold.RTM. Strong by BASF, copolymers derived
from crotonic acid, such as the vinyl acetate/vinyl
tert-butylbenzoate/crotonic acid terpolymers and the crotonic
acid/vinyl acetate/vinyl neododecanoate terpolymers sold, for
example, under the name Resin 28-29-30 by National Starch, polymers
derived from maleic, fumaric or itaconic acids or anhydrides with
vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives,
or acrylic acid and its esters, such as the monoesterified methyl
vinyl ether/maleic anhydride copolymers sold, for example, under
the name Gantrez.RTM. by ISP, the copolymers of methacrylic acid
and of methyl methacrylate sold under the name Eudragit.RTM. L by
Rohm Pharma, the copolymers of methacrylic acid and of ethyl
acrylate sold under the name Luvimer.RTM. MAEX or MAE by BASF, the
vinyl acetate/crotonic acid copolymers sold under the name Luviset
CA 66 by BASF, the vinyl acetate/crotonic acid copolymers grafted
by polyethylene glycol sold under the name Aristoflex.RTM. A by
BASF or the polymer sold under the name Fixate G-100 by Noveon.
[0067] In at least one embodiment, among the anionic fixing
polymers mentioned above, one or more of the following polymers may
be used: the monoesterified methyl vinyl ether/maleic anhydride
copolymers sold under the name Gantrez.RTM. ES 425 by ISP, the
acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers sold
under the name Ultrahold.RTM. Strong by BASF, the copolymers of
methacrylic acid and of methyl methacrylate sold under the name
Eudragit.RTM. L by Rohm Pharma, the vinyl acetate/vinyl
tert-butyl-benzoate/crotonic acid terpolymers and the crotonic
acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the
name Resin 28-29-30 by National Starch, the copolymers of
methacrylic acid and of ethyl acrylate sold under the name
Luvimer.RTM. MAEX or MAE by BASF, the vinylpyrrolidone/acrylic
acid/lauryl methacrylate terpolymers sold under the name
Acrylidone.RTM. LM by ISP or the polymer sold under the name Fixate
G-100 by Noveon.
Cationic Fixing Polymers
[0068] The film-forming cationic fixing polymers which can be used
according to the present invention are, in at least one embodiment,
chosen from polymers comprising primary, secondary, tertiary and/or
quaternary amine groups forming part of the polymer chain or
directly connected to the latter and having a molecular weight
ranging from 500 to 5,000,000, such as from 1000 to 3,000,000.
[0069] In at least one embodiment, the cationic fixing polymers are
chosen from homopolymers and copolymers of acrylic and methacrylic
esters and amides comprising aminated functional groups, cationic
polysaccharides, quaternary copolymers of vinylpyrrolidone and of
vinylimidazole, and chitosans.
[0070] Mention may be made, among these polymers, of the following
cationic polymers:
[0071] (1) Homopolymers or copolymers derived from acrylic or
methacrylic esters or amides comprising at least one of the units
of following formulae: ##STR2## in which
[0072] R.sub.3 is chosen from a hydrogen atom and a CH.sub.3
radical;
[0073] A is chosen from a linear or branched alkyl group comprising
from 1 to 6 carbon atoms and a hydroxyalkyl group comprising from 1
to 4 carbon atoms;
[0074] R.sub.4, R.sub.5 and R.sub.6, which are identical or
different, are each individually chosen from an alkyl group having
from 1 to 18 carbon atoms and a benzyl radical;
[0075] R.sub.1 and R.sub.2, which are identical or different, each
are individually chosen from a hydrogen atom and an alkyl group
having from 1 to 6 carbon atoms;
[0076] X is chosen from a methyl sulphate anion and a halide, such
as chloride or bromide.
[0077] The copolymers of family (1) additionally comprise at least
one unit deriving from comonomers which can be chosen from the
family of the acrylamides, methacrylamides, diacetone acrylamides,
acrylamides and methacrylamides substituted on the nitrogen by
lower (C.sub.1-C.sub.4) alkyl groups, groups derived from acrylic
or methacrylic acids or their esters, vinyllactams, such as
vinylpyrrolidone or vinylcaprolactam, or vinyl esters.
[0078] Thus, mention may be made, among these copolymers of family
(1), of:
[0079] copolymers of acrylamide and of dimethylaminoethyl
methacrylate which is quaternized with dimethyl sulphate or with a
methyl halide, such as that sold under the name Hercofloc.RTM. by
Hercules,
[0080] copolymers of acrylamide and of
methacryloyloxyethyltrimethylammonium chloride, disclosed, for
example, in Patent Application EP-A-080 976 and sold under the name
Bina Quat P 100 by Ciba-Geigy,
[0081] copolymer of acrylamide and of
methacryloyloxyethyltrimethylammonium methyl sulphate, such as that
sold under the name Reten by Hercules,
[0082] vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate
copolymers, which may or may not be quaternized, such as the
products sold under the name "Gafquat.RTM." by ISP, like for
example "Gafquat.RTM. 734" or "Gafquat.RTM. 755", or the products
named "Copolymer.RTM. 845, 958 and 937". These polymers are
described in detail in French Patents 2 077 143 and 2 393 573,
[0083] polymers comprising a fatty chain and comprising a
vinylpyrrolidone unit, such as the products sold under the name
Styleze W2O and Styleze W10 by ISP,
[0084] dimethylaminoethyl
methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as
the product sold under the name Gaffix VC 713 by ISP, and
[0085] quaternized
vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers, such
as the products sold under the name "Gafquat.RTM. HS 100" by
ISP.
[0086] (2) Cationic polysaccharides, for example comprising
quaternary ammonium, such as those disclosed in U.S. Pat. Nos.
3,589,578 and 4,031,307, such as guar gums comprising
trialkylammonium cationic groups. Such products are sold, for
instance, under the trade names Jaguar C13 S, Jaguar C15 and Jaguar
C17 by Meyhall.
[0087] (3) Quaternary copolymers of vinylpyrrolidone and of
vinylimidazole.
[0088] (4) Chitosans or their salts; the salts which can be used
are, for example, chitosan acetate, lactate, glutamate, gluconate
or pyrrolidonecarboxylate. Mention may made, among these compounds,
of the chitosan having a degree of deacetylation of 90.5% by weight
sold under the name Kytan Brut Standard by Aber Technologies or the
chitosan pyrrolidonecarboxylate sold under the name Kytamer.RTM. PC
by Amerchol.
[0089] (5) Cationic cellulose derivatives, such as the copolymers
of cellulose or of cellulose derivatives grafted with a
water-soluble monomer comprising a quaternary ammonium and
disclosed, for instance, in U.S. Pat. No. 4,131,576, such as
hydroxyalkylcelluloses, for example hydroxymethyl-, hydroxyethyl-
or hydroxypropylcelluloses, grafted, for example, with a
methacryloyloxyethyltrimethylammonium,
methacrylamidopropyltrimethylammonium or dimethyidiallylammonium
salt.
[0090] The marketed products corresponding to this definition
include, for example, the products sold under the name "Celquat L
200" and "Celquat H 100" by National Starch.
Amphoteric Fixing Polymers
[0091] The amphoteric fixing polymers which can be used in
accordance with the present disclosure can be chosen from polymers
comprising B and C units distributed randomly in the polymer chain,
where B denotes a unit deriving from a monomer comprising at least
one basic nitrogen atom and C denotes a unit deriving from an
acidic monomer comprising at least one group chosen from carboxyl
and sulpho groups or else B and C can denote groups deriving from
zwitterionic carboxybetaine or sulphobetaine monomers;
[0092] B and C can also denote a cationic polymer chain comprising
primary, secondary, tertiary or quaternary amine groups, in which
at least one of the amine groups carries a carboxyl or sulpho group
connected via a hydrocarbon group, or else B and C form part of a
chain of a polymer comprising an .alpha.,.beta.-dicarboxyethylene
unit, one of the carboxyl groups of which has been reacted with a
polyamine comprising at least one primary or secondary amine
groups.
[0093] In at least one embodiment, the amphoteric fixing polymers
are chosen from copolymers comprising acidic vinyl units and
comprising basic vinyl units, acylated and crosslinked
polyaminoamides, polymers comprising zwitterionic units, polymers
derived from chitosan, modified (C.sub.1-C.sub.5)alkyl vinyl
ether/maleic anhydride copolymers, amphoteric polyurethanes and
amphoteric grafted silicone polymers.
[0094] Examples of amphoteric fixing polymers corresponding to the
definition given above and used in at least one embodiment herein
are chosen from the following polymers:
[0095] 1) copolymers comprising acidic vinyl units and comprising
basic vinyl units, such as those resulting from the
copolymerization of a monomer derived from a vinyl compound
carrying a carboxyl group, such as acrylic acid, methacrylic acid,
maleic acid or .alpha.-chloracrylic acid, and of a basic monomer
derived from a substituted vinyl compound comprising at least one
basic atom, such as dialkylaminoalkyl methacrylate and acrylate or
dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds are
disclosed, for example, in U.S. Pat. No. 3,836,537.
[0096] 2) Polymers comprising units deriving:
[0097] a) from at least one monomer chosen from acrylamides or
methacrylamides substituted on the nitrogen atom by an alkyl
group,
[0098] b) from at least one acidic comonomer comprising one or more
reactive carboxyl groups, and
[0099] c) from at least one basic comonomer, such as esters
comprising primary, secondary, tertiary and quaternary amine
substituents of acrylic and methacrylic acids and the
quaternization product of dimethylaminoethyl methacrylate with
dimethyl or diethyl sulphate.
[0100] In at least one embodiment, the N-substituted acrylamides or
methacrylamides used according to the present disclosure are the
compounds in which the alkyl groups comprise from 2 to 12 carbon
atoms and more particularly N-ethylacrylamide,
N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide,
N-decylacrylamide or N-dodecylacrylamide, and the corresponding
methacrylamides.
[0101] The acidic comonomers may be, for example, chosen from
acrylic, methacrylic, crotonic, itaconic, maleic or fumaric acids
and alkyl monoesters having 1 to 4 carbon atoms of maleic or
fumaric acids or anhydrides.
[0102] The basic comonomers may be, for example, chosen from
aminoethyl, butylaminoethyl, N,N'-dimethylaminoethyl and
N-tert-butylaminoethyl methacrylates.
[0103] Use may be made, in at least one embodiment, of one or more
copolymers for which the CTFA name (4th Ed., 1991) is
Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer,
such as the products sold under the name Amphomer.RTM. or
Lovocryl.RTM. 47 by National Starch.
[0104] (3) Partially or completely acylated and crosslinked
polyaminoamides deriving from polyaminoamides of formula: ##STR3##
in which
[0105] R.sub.10 is a divalent group derived from a saturated
dicarboxylic acid, from an aliphatic mono- or dicarboxylic acid
comprising an ethylenic double bond, from an ester of a lower
alkanol having 1 to 6 carbon atoms of these acids, or from a group
deriving from the addition of any one of the said acids with a
bis-primary or bis-secondary amine, and
[0106] Z is a group deriving from a bis-primary, mono- or
bis-secondary polyalkylenepolyamine and, in at least one
embodiment, represents:
[0107] a) in the amount of 60 to 100 mol %, the group ##STR4##
where x=2 and p=2 or 3, or else x=3 and p=2 this group deriving
from diethylenetriamine, triethylenetetraamine or
dipropylenetriamine;
[0108] b) in the amount of 0 to 40 mol %, the above group (III), in
which x=2 and p=1 and which derives from ethylenediamine, or the
group deriving from piperazine: ##STR5##
[0109] c) in the amount of 0 to 20 mol %, the group
--NH--(CH.sub.2).sub.6--NH-- deriving from hexamethylenediamine,
these polyaminoamides being crosslinked by addition reaction of a
bifunctional crosslinking agent chosen from epihalohydrins,
diepoxides, dianhydrides or bis-unsaturated derivatives, by means
of 0.025 to 0.35 mol of crosslinking agent per amine group of the
polyaminoamide, and acylated by reaction with acrylic acid,
chloroacetic acid or an alkanesultone or their salts.
[0110] The saturated carboxylic acids may be, for example, chosen
from acids having 6 to 10 carbon atoms, such as adipic,
2,2,4-trimethyladipic or 2,4,4-trimethyladipic, or terephthalic
acids, and the acids comprising an ethylenic double bond, such as,
for example, acrylic, methacrylic or itaconic acids.
[0111] The alkanesultones used in the acylation may be propane- or
butanesultone and the salts of the acylating agents are, for
example, the sodium or potassium salts.
[0112] (4) Polymers comprising zwitterionic units of formula:
##STR6## in which
[0113] R.sub.11 is a polymerizable unsaturated group, such as an
acrylate, methacrylate, acrylamide or methacrylamide group,
[0114] y and z are each independently an integer from 1 to 3,
[0115] R.sub.12 and R.sub.13 are each independently chosen from a
hydrogen atom and from methyl, ethyl and propyl groups, and
[0116] R.sub.14 and R.sub.15 are each independently chosen from a
hydrogen atom and an alkyl group such that the sum of the carbon
atoms in R.sub.14 and R.sub.15 does not exceed 10.
[0117] The polymers comprising such units can also comprise units
derived from non-zwitterionic monomers, such as dimethyl- or
diethylaminoethyl acrylate or methacrylate or alkyl acrylates or
methacrylates, acrylamides or methacrylamides, or vinyl
acetate.
[0118] Mention may be made, by way of example, of methyl
methacrylate/dimethylcarboxymethylammonioethyl methacrylate
copolymers, such as the product sold under the name Diaformer Z301
by Sandoz.
[0119] (5) Polymers derived from chitosan comprising monomer units
corresponding to the following formulae: ##STR7## the unit (D)
being present in an amount of from 0 to 30%, the unit (E) being
present in an amount of from 5 to 50% and the unit (F) being
present in an amount of from 30 to 90%, it being understood that,
in this unit (F), R.sub.16 is a group of formula: ##STR8## in
which, if q=0, R.sub.17, R.sub.18 and R.sub.19, which are identical
or different, each are chosen from a hydrogen atom and from
residues chosen from methyl, hydroxyl, acetoxy, amino,
monoalkylamine, and dialkylamine residues, optionally interrupted
by at least one nitrogen atom and/or optionally substituted by at
least one group chosen from amine, hydroxyl, carboxyl, alkylthio
and sulpho groups, or by an alkylthio residue in which the alkyl
group carries an amino residue, at least one of the R.sub.17,
R.sub.18 and R.sub.19 groups being, in this case, a hydrogen
atom;
[0120] or, if q=1, R.sub.17, R.sub.18 and R.sub.19 are each
independently chosen from a hydrogen atom, and the salts formed by
these compounds with bases or acids.
[0121] (6) Polymers corresponding to the formula (V), for example
disclosed in French Patent FR 1 400 366: ##STR9## in which
[0122] R.sub.20 is chosen from a hydrogen atom, a CH.sub.3O,
CH.sub.3CH.sub.2O group, and a phenyl group,
[0123] R.sub.21 is chosen from a hydrogen atom and a lower alkyl
group, such as methyl or ethyl,
[0124] R.sub.22 is chosen from a hydrogen atom and a lower
C.sub.1-C.sub.6 alkyl group, such as methyl or ethyl,
[0125] R.sub.23 is chosen from a lower C.sub.1-C.sub.6 alkyl group,
such as methyl or ethyl, and a group corresponding to the formula:
--R.sub.24--N(R.sub.22).sub.2, wherein R.sub.24 is chosen from a
--CH.sub.2--CH.sub.2 group, a --CH.sub.2--CH.sub.2--CH.sub.2--
group, and a --CH.sub.2--CH(CH.sub.3)-- group and R.sub.22 having
the meanings mentioned above,
[0126] R.sub.24 is chosen from a --CH.sub.2--CH.sub.2-- group, a
--CH.sub.2--CH.sub.2--CH.sub.2-- group, and a
--CH.sub.2--CH(CH.sub.3)-- group, and
[0127] r is an integer greater or equal to 1.
[0128] (7) Polymers derived from the N-carboxyalkylation of
chitosan, such as the N-(carboxymethyl)chitosan or the
N-(carboxybutyl)chitosan sold under the name "Evalsan" by Jan
Dekker.
[0129] (8) Amphoteric polymers of the -D-X-D-X-- type chosen
from:
[0130] a) polymers obtained by reaction of chloroacetic acid or
sodium chloroacetate with compounds comprising at least one unit of
formula: -D-X-D-X-D- (VI) where D is a group ##STR10## and X
denotes the symbol E or E', E or E', which are identical or
different, denoting a bivalent group which is a straight- or
branched-chain alkylene group comprising up to 7 carbon atoms in
the main chain which is unsubstituted or substituted by hydroxyl
groups and which can additionally comprise oxygen, nitrogen or
sulphur atoms or 1 to 3 aromatic and/or heterocyclic rings; the
oxygen, nitrogen and sulphur atoms being present in the form of
ether, thioether, sulphoxide, sulphone, sulphonium, alkylamine or
alkenylamine groups or hydroxyl, benzylamine, amine oxide,
quaternary ammonium, amide, imide, alcohol, ester and/or urethane
groups.
[0131] b) polymers of formula: -D-X-D-X-- (VI') where D denotes a
group ##STR11## and X denotes the symbol E or E' and at least once
E', E having the meaning indicated above and E' being a bivalent
group which is a straight- or branched-chain alkylene group having
up to 7 carbon atoms in the main chain which is unsubstituted or
substituted by at least one hydroxyl group and which comprises at
least one nitrogen atom, the at least one nitrogen atom being
substituted by an alkyl chain optionally interrupted by an oxygen
atom and necessarily comprising at least one carboxyl functional
group and at least one hydroxyl functional group and betainized by
reaction with chloroacetic acid or sodium chloroacetate.
[0132] (9) (C.sub.1-C.sub.5)Alkyl vinyl ether/maleic anhydride
copolymers partially modified by semiamidation with an
N,N-dialkylaminoalkylamine, such as N,N-dimethylamino-propylamine,
or by semiesterification with an N,N-dialkylaminoalkanol. These
copolymers can also comprise other vinyl comonomers, such as
vinylcaprolactam.
[0133] In at least one embodiment of the present disclosure, the
amphoteric fixing polymers used one or more chosen from family (3),
such as the copolymers with the CTFA name of
Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer,
such as the products sold under the names Amphomer.RTM.,
Amphomer.RTM. LV 71 or Lovocryl.RTM. 47 by National Starch, and
those of family.(4), such as methyl
methacrylate/dimethylcarboxy-methylammonioethyl methacrylate
copolymers, sold, for example, under the name Diaformer Z301 by
Sandoz.
Nonionic Fixing Polymers
[0134] The nonionic fixing polymers which can be used according to
the present disclosure are chosen, for example, from:
[0135] polyalkyloxazolines;
[0136] vinyl acetate homopolymers;
[0137] vinyl acetate copolymers, such as, for example copolymers of
vinyl acetate and of acrylic ester, copolymers of vinyl acetate and
of ethylene, or copolymers of vinyl acetate and of maleic ester,
for example of dibutyl maleate;
[0138] acrylic ester homopolymers and copolymers, such as, for
example, copolymers of alkyl acrylates and of alkyl methacrylates,
such as the products provided by Rohm & Haas under the names
Primal.RTM. AC-261 K and Eudragit.RTM. NE 30 D, by BASF under the
name 8845 or by Hoechst under the name Appretan.RTM. N9212;
[0139] copolymers of acrylonitrile and of a nonionic monomer
chosen, for example, from butadiene and alkyl (meth)acrylates;
mention may be made of the products provided under the name CJ 0601
B by Rohm & Haas;
[0140] styrene homopolymers;
[0141] styrene copolymers, such as, for example, copolymers of
styrene and of alkyl (meth)acrylate, such as the products
Mowilith.RTM. LDM 6911, Mowilith.RTM. DM 611 and Mowilith.RTM. LDM
6070 provided by Hoechst or the products Rhodopas.RTM. SD 215 and
Rhodopas.RTM. DS 910 provided by Rhone-Poulenc, copolymers of
styrene, of alkyl methacrylate and of alkyl acrylate, copolymers of
styrene and of butadiene or copolymers of styrene, of butadiene and
of vinylpyridine;
[0142] polyamides;
[0143] vinyllactam homopolymers other than vinylpyrrolidone
homopolymers, such as the polyvinylcaprolactam sold under the name
Luviskol.RTM. Plus by BASF; and
[0144] vinyllactam copolymers, such as the
poly(vinylpyrrolidone/vinyllactam) copolymer sold under the trade
name Luvitec.RTM. VPC 55K65W by BASF, poly(vinylpyrrolidone/vinyl
acetate) copolymers, such as those sold under the name PVPVA.RTM.
S630L by ISP or Luviskol.RTM. VA 73, VA 64, VA 55, VA 37 and VA 27
by BASF, and poly(vinylpyrrolidone/vinyl acetate/vinyl propionate)
terpolymers, such as, for example, that sold under the name
Luviskol.RTM. VPA 343 by BASF.
[0145] The alkyl groups of the nonionic polymers mentioned above
may, in at least one embodiment, have from 1 to 6 carbon atoms.
Grafted Silicone Fixing Polymers
[0146] According to the present disclosure, it is also possible to
use fixing polymers of grafted silicone type comprising a
polysiloxane part and a part composed of a silicone-free organic
chain, one of the two parts constituting the main chain of the
polymer and the other being grafted onto the main chain. The
polymers of this type may be amphoteric, anionic or non-ionic. In
at least one embodiment, the grafted silicone polymers are anionic
or nonionic.
[0147] These polymers are disclosed, for example, in Patent
Applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105, WO
95/00578, EP-A-0 582 152 and WO 93/23009 and U.S. Pat. Nos.
4,693,935, 4,728,571 and 4,972,037.
[0148] Such polymers are, for example, the copolymers capable of
being obtained by radical polymerization from the mixture of
monomers formed from:
[0149] a) 50 to 90% by weight of tert-butyl acrylate,
[0150] b) 0 to 40% by weight of acrylic acid,
[0151] c) 5 to 40% by weight of a silicone macromer of formula:
##STR12## where v is a number ranging from 5 to 700, the
percentages by weight being calculated with respect to the total
weight of the monomers.
[0152] Other examples of grafted silicone polymers are in
particular polydimethylsiloxanes (PDMSs) on which are grafted, via
a connecting link of thiopropylene type, mixed polymer units of the
poly((meth)acrylic acid) type and of the poly(alkyl (meth)acrylate)
type and polydimethylsiloxanes (PDMSs) on which are grafted, via a
connecting link of thiopropylene type, polymer units of the
poly(isobutyl (meth)acrylate) type.
[0153] Mention may be made, as another type of silicone fixing
polymers, of the product Luviflex.RTM. Silk sold by BASF.
Polyurethane Fixing Polymers
[0154] Use may also be made, as fixing polymers, of cationic,
nonionic, anionic or amphoteric polyurethanes which may or may not
be functionalized and which may or may not be silicone-comprising,
or their mixtures.
[0155] The polyurethanes useful in at least some embodiments of the
present disclosure are those disclosed in Applications EP 0 751
162, EP 0 637 600, EP 0 648 485 and FR 2 743 297, assigned to
L'Oreal, and in Applications EP 0 656 021 and WO 94/03510 of BASF
and EP 0 619 111 of National Starch.
[0156] Mention may be made, as polyurethanes suitable in at least
one embodiment of the present disclosure, of the products sold
under the names Luviset PUR.RTM. and Luviset.RTM. Si PUR by
BASF.
[0157] When the composition according to the present disclosure
comprises at least one additional fixing polymer, the concentration
of the at least one polymer ranges from 0.1 to 20%, for example
from 0.5 to 10%, by weight with respect to the total weight of the
composition.
[0158] The compositions according to the present disclosure can
also comprise, as additional cosmetic adjuvant, at least one
additional thickening polymer, also referred to as
"rheology-adjusting agent", other than the modified guar gums.
[0159] The rheology-adjusting agents can be chosen from fatty acid
amides (coconut diethanol- or monoethanolamide, oxyethylenated
alkyl ether carboxylic acid monoethanolamide), cellulose thickeners
(hydroxyethylcellulose, hydroxypropylcellulose,
carboxymethylcellulose), gums of microbial origin (xanthan gum,
scleroglucan gum), crosslinked homopolymers of acrylic acid or of
acrylamidopropanesulphonic acid, and associative polymers.
[0160] The associative polymers which can be used herein are
water-soluble polymers capable, in an aqueous medium, of reversibly
associating with one another or with other molecules. Their
chemical structure comprises hydrophilic regions and hydrophobic
regions characterized by at least one fatty chain.
[0161] The associative polymers which can be used herein can be of
anionic, cationic, amphoteric or nonionic type.
[0162] The concentration of additional thickening polymer(s) ranges
from 0.01 to 20%, such as from 0.05 to 10%, by weight with respect
to the total weight of the composition.
[0163] The compositions according to the present disclosure can
also comprise, as additional cosmetic adjuvant, at least one
compound chosen from silicones, silicone-comprising fatty
substances and silicone-free fatty substances.
[0164] The silicones which can be used in the compositions
according to the present disclosure can be linear, cyclic, branched
or unbranched and volatile or nonvolatile. They can be in the
soluble, dispersed or microdispersed form and can be provided in
the form of oils, resins or gums. They can, for example, be
polyorganosiloxanes which are insoluble in the cosmetically
acceptable medium.
[0165] Organopolysiloxanes are defined in more detail in the work
by Walter Noll, "Chemistry and Technology of Silicones" (1968),
Academic Press. They can be volatile or nonvolatile.
[0166] When they are volatile, the silicones are chosen, for
example, from those having a boiling point ranging from 60.degree.
C. to 260.degree. C. and, in at least one embodiment, from:
[0167] (i) cyclic silicones comprising from 3 to 7 silicon atoms,
such as from 4 to 5 silicon atoms. They are, for example,
octamethylcyclotetrasiloxane, sold, for instance, under the name of
"Volatile Silicone 7207" by Union Carbide or "Silbione 70045 V 2"
by Rhodia, decamethylcyclopentasiloxane, sold under the name of
"Volatile Silicone 7158" by Union Carbide or "Silbione 70045 V 5"
by Rhodia, and their mixtures.
[0168] Mention may also be made of cyclocopolymers of the
dimethylsiloxane/methylalkylsiloxane type, such as "Silicone
Volatile FZ 3109", sold by Union Carbide, with the chemical
structure: ##STR13##
[0169] Mention may also be made of mixtures of cyclic silicones
with silicon-derived organic compounds, such as the mixture of
octamethylcyclotetrasiloxane and of
tetratrimethylsilylpentaerythritol (50/50) and the mixture of
octamethylcyclotetrasiloxane and of
1,1'-oxy(2,2,2',2',3,3'-hexatrimethylsilyloxy)bisneopentane;
[0170] (ii) linear volatile silicones having 2 to 9 silicon atoms
and having a viscosity of less than or equal to 5.times.10.sup.-6
m.sup.2/s at 25.degree. C. Such silicones include, for example,
decamethyltetrasiloxane, sold in particular under the name "SH 200"
by Toray Silicone. Silicones coming within this class are also
described in the article published in Cosmetics and Toiletries,
Vol. 91, Jan. 76, p. 27-32, Todd & Byers, "Volatile Silicone
Fluids for Cosmetics".
[0171] Mention may, for example, be made, among nonvolatile
silicones, of polyalkylsiloxanes, polyarylsiloxanes,
polyalkylarylsiloxanes, silicone gums and resins,
polyorganosiloxanes modified by organofunctional groups, and their
mixtures.
[0172] The organomodified silicones which can be used in accordance
with the present disclosure are silicones as defined above
comprising, in their structure, at least one organofunctional group
attached via a hydrocarbon group.
[0173] Mention may be made, among organomodified silicones, of
polyorganosiloxanes comprising:
[0174] polyethyleneoxy and/or polypropyleneoxy groups optionally
comprising C.sub.6-C.sub.24 alkyl groups, such as the products
named dimethicone copolyol sold by Dow Corning under the name DC
1248 or the oils Silwet.RTM. L 722, L 7500, L 77 or L 711 from
Union Carbide and the (C.sub.12)alkyl methicone copolyol sold by
Dow Corning under the name Q2 5200;
[0175] substituted or unsubstituted aminated groups, such as the
products sold under the names GP 4 Silicone Fluid and GP 7100 by
Genesee or the products sold under the names Q2 8220 and Dow
Corning 929 or 939 by Dow Corning. The substituted aminated groups
are in particular C.sub.1-C.sub.4 aminoalkyl groups;
[0176] thiol groups, such as the products sold under the names "GP
72 A" and "GP 71" from Genesee;
[0177] alkoxylated groups, such as the product sold under the name
"Silicone Copolymer F-755" by SWS Silicones and Abil Wax.RTM. 2428,
2434 and 2440 by Goldschmidt;
[0178] hydroxylated groups, such as the polyorganosiloxanes
comprising a hydroxyalkyl functional group disclosed in French
Patent Application FR-A-85 16334;
[0179] acyloxyalkyl groups, such as, for example, the
polyorganosiloxanes disclosed in U.S. Pat. No. 4,957,732;
[0180] anionic groups of the carboxylic acid type, such as, for
example, in the products disclosed in Patent EP 186 507 from Chisso
Corporation, or of the alkylcarboxyl type, such as those present in
the product X-22-3701 E from Shin-Etsu; 2-hydroxyalkylsulphonate
type; or 2-hydroxyalkyl thiosulphate type, such as the products
sold by Goldschmidt under the names "Abil.RTM. S201" and "Abil.RTM.
S255";
[0181] hydroxyacylamino groups, such as the polyorganosiloxanes
disclosed in Application EP 342 834. Mention may be made, for
example, of the product Q2-8413 from Dow Corning.
[0182] The silicone oils which can be used in the compositions
according to the present disclosure are volatile or nonvolatile
polymethylsiloxanes comprising a linear or cyclic silicone chain
which are liquid or pasty at ambient temperature, for example
cyclopolydimethylsiloxanes (cyclomethicones), such as
cyclohexasiloxane; polydimethylsiloxanes comprising pendant alkyl,
alkoxy or phenyl groups or alkyl, alkoxy or phenyl groups at the
end of the silicone chain, which groups have from 2 to 24 carbon
atoms; phenylated silicones, such as phenyl trimethicones, phenyl
dimethicones, phenyl-(trimethylsiloxy)diphenylsiloxanes, diphenyl
dimethicones, diphenyl(methyidiphenyl)trisiloxanes,
(2-phenylethyl)trimethylsiloxysilicates or
polymethyl-phenylsiloxanes; and their mixtures.
[0183] The silicone gums which can be used in the compositions
according to the present disclosure are polydiorganosiloxanes of
high molecular mass, i.e., ranging from 200,000 to 2,000,000,.used
alone or as a mixture in a solvent chosen from volatile silicones,
polydimethylsiloxane oils, polymethylphenylsiloxane oils,
polydiphenyl-dimethylsiloxane oils, isoparaffins, methylene
chloride, pentane, hydrocarbons and their mixtures.
[0184] In at least one embodiment, use is made of a silicone gum
with a molecular weight of less than 1,500,000. The silicone gums
are, for example, polydimethylsiloxanes, polyphenylmethylsiloxanes,
poly(diphenylsiloxane/dimethylsiloxane)s,
poly(dimethyl-siloxane/methylvinylsiloxane)s,
poly(dimethylsiloxane/phenylmethylsiloxane)s or
poly(diphenylsiloxane/dimethylsiloxane/methylvinylsiloxane)s.
[0185] These silicone gums can be terminated at the chain end by
trimethylsilyl or dimethylhydroxysilyl groups.
[0186] The silicone resins which can be used in the compositions
according to the present disclosure are crosslinked siloxane
systems including the units R.sub.2SiO.sub.2/2, RSiO.sub.3/2 and
SiO.sub.4/2 in which R is chosen from a hydrocarbon group having
from 1 to 6 carbon atoms and from a phenyl group. In at least one
embodiment, R is chosen from a lower (C.sub.1-C.sub.6) alkyl
radical and a phenyl radical.
[0187] The silicone-free fatty substances which can be used in the
compositions according to the present disclosure are all the
organic or inorganic, natural or synthetic, silicone-free oils,
waxes or resins.
[0188] An oil within the meaning of the present disclosure is a
lipophilic compound which is liquid at ambient temperature
(approximately 25.degree. C.) and which exhibits a reversible
solid/liquid change in state. Animal and vegetable oils comprise,
as essential constituents, triesters of propane-1,2,3-triol.
[0189] Mention may be made, as oils which can be used in the
composition of the present disclosure, for example of:
[0190] hydrocarbon oils of animal origin, such as
perhydrosqualene;
[0191] hydrocarbon oils of vegetable origin, such as liquid
triglycerides of fatty acids comprising from 4 to 10 carbon atoms,
such as triglycerides of heptanoic or octanoic acids, or also, for
example, sunflower,.maize, soybean, cucumber, grape seed, sesame,
hazelnut, apricot, macadamia, arara, castor or avocado oils,
triglycerides of caprylic/capric acids, such as, for example, those
sold by Stearineries Dubois or those sold under the names Miglyol
810, 812 and 818 by Dynamit Nobel, jojoba oil or shea butter
oil;
[0192] synthetic esters and ethers, such as of fatty acids, such as
the oils of formulae R.sup.6COOR.sup.7 and R.sup.6OR.sup.7 in which
R.sup.6 is the residue of a fatty acid comprising from 8 to 29
carbon atoms and R.sup.7 is a branched or unbranched hydrocarbon
chain comprising from 3 to 30 carbon atoms, such as, for example,
purcellin oil, isononyl isononanoate, isopropyl myristate,
2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyidodecyl
erucate or isostearyl isostearate; hydroxylated esters, such as
isostearyl lactate, octyl hydroxystearate, octyldodecyl
hydroxystearate, diisostearyl malate or triisocetyl citrate;
heptanoates, octanoates or decanoates of fatty alcohols; polyol
esters, such as propylene glycol dioctanoate, neopentyl glycol
diheptanoate and diethylene glycol diisononanoate; and
pentaerythritol esters, such as pentaerythrityl
tetraisostearate;
[0193] linear or branched hydrocarbons of mineral or synthetic
origin, such as volatile or nonvolatile liquid paraffins and their
derivatives, liquid petrolatum, polydecenes or hydrogenated
polyisobutene, such as parleam oil;
[0194] fluid fatty alcohols having from 8 to 26 carbon atoms, such
as octyldodecanol, 2-butyloctanol, oleyl alcohol, linoleyl alcohol
or linolenyl alcohol;
[0195] alkoxylated, such as ethoxylated, fatty alcohols, such as
oleth-12;
[0196] partially hydrocarbon-comprising fluorinated oils, such as
those disclosed in the document JP-A-2 295912. Mention may also be
made, as fluorinated oils, of perfluoromethylcyclopentane and
perfluoro(1,3-dimethylcyclohexane), for example sold under the
names "Flutec PC1.RTM." and "Flutec PC3.RTM." by BNFL
Fluorochemicals; perfluoro(1,2-dimethylcycobutane);
perfluoroalkanes, such as dodecafluoropentane and
tetradecafluorohexane, for example sold under the names "PF
5050.RTM." and "PF 5060.RTM." by 3M, or else bromoperfluorooctane,
for example sold under the name "Foralkyl.RTM." by Atochem;
nonafluoromethoxybutane, for example sold under the name "MSX
4518.RTM." by 3M, and nonafluoroethoxyisobutane; or
perfluoromorpholine derivatives, such as
4-(trifluoromethyl)perfluoromorpholine, for example sold under the
name "PF 5052.RTM." by 3M.
[0197] The term "hydrocarbon oil" in the list of the oils mentioned
above is understood to mean any oil comprising predominantly carbon
and hydrogen atoms and optionally ester, ether, fluoro, carboxylic
acid and/or alcohol groups.
[0198] A wax within the meaning of the present disclosure is a
lipophilic compound which is solid at ambient temperature
(approximately 25.degree. C.), which exhibits a reversible
solid/liquid change in state, which has a melting point of greater
than approximately 40.degree. C. which can range up to 200.degree.
C. and which exhibits an anisotropic crystalline arrangement in the
solid state. Animal and vegetable waxes comprise, as essential
constituents, esters of carboxylic acids and of long-chain
alcohols. Generally, the size of the crystals of the wax is such
that the crystals diffract and/or scatter light, conferring a more
or less opaque cloudy appearance on the composition which comprises
them. On bringing the wax to its melting point, it is possible to
render it miscible with oils and to form a microscopically
homogeneous mixture but, on bringing the temperature of the mixture
back to ambient temperature, recrystallization of the wax in the
oils of the mixture is obtained, which recrystallization can be
detected microscopically and macroscopically (opalescence).
[0199] Mention may be made, as waxes which can be used in the
present disclosure, of waxes of animal origin, such as beeswax,
spermaceti, lanolin wax and lanolin derivatives; vegetable waxes,
such as sunflower, rice or apple peel waxes, carnauba wax,
candelilla wax, ouricury wax, Japan wax, cocoa butter or cork fibre
or sugarcane waxes; mineral waxes, for example paraffin wax,
petrolatum wax, lignite wax or microcrystalline waxes, ceresin or
ozokerite; synthetic waxes, such as polyethylene waxes or
Fischer-Tropsch waxes; and their mixtures.
[0200] The concentration of compound(s) chosen from silicones,
silicone-comprising fatty substances and silicone-free fatty
substances can range from 0.01 to 20%, such as from 0.05 to 10%, by
weight with respect to the total weight of the composition.
[0201] The styling composition according to the present disclosure
can additionally comprise at least one additive chosen from
nonionic, anionic, cationic and amphoteric surface-active agents,
additional nonionic, anionic, cationic and amphoteric polymers
other than the fixing polymers used in the compositions according
to the invention, ceramides and pseudoceramides, vitamins and
provitamins, including panthenol, water-soluble and fat-soluble
sunscreen-agents which may or may not comprise silicone, solid
fillers and particles, such as, for example, inorganic and organic
pigments which may or may not be coloured, pearlescent and
opacifying agents, glitter, active particles, dyes, sequestering
agents, plasticizing agents, solubilizing agents, acidifying
agents, basifying agents, neutralizing agents, inorganic and
organic thickening agents, antioxidants, hydroxy acids, penetrating
agents, fragrances and preservatives.
[0202] A person skilled in the art will take care to choose the
optional additives and their amounts so that they do not harm the
properties of the compositions disclosed herein.
[0203] These additives can be present in the composition according
to the present disclosure in an amount ranging from 0 to 20% by
weight, with respect to the total weight of the composition.
[0204] Other than in the examples, or where otherwise indicated,
all numbers expressing quantities of ingredients, reaction
conditions, and so forth used in the specification and claims are
to be understood as being modified in all instances by the term
"about." Accordingly, unless indicated to the contrary, the
numerical parameters set forth in the specification and attached
claims are approximations that may vary depending upon the desired
properties sought to be obtained by the present invention. At the
very least, and not as an attempt to limit the application of the
doctrine of equivalents to the scope of the claims, each numerical
parameter should be construed in light of the number of significant
digits and ordinary rounding approaches.
[0205] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention are approximations,
unless otherwise indicated the numerical values set forth in the
specific examples are reported as precisely as possible. Any
numerical value, however, inherently contain certain errors
necessarily resulting from the standard deviation found in their
respective testing measurements.
[0206] The following examples illustrate the present invention and
should not be regarded in any way as limiting the invention.
EXAMPLES
[0207] The following formulations A and B were prepared
TABLE-US-00001 as % of active material Formulation A
Diglycol/CHDM/Isophthalates/SIP copolymer 20 (Eastman AQ 55 S -
Eastman) Hydroxypropyl guar (Jaguar HP 105 - Rhodia) 1.5 Carbomer
(Carbopol Ultrez 10 - Noveon) 0.25 Deionized water q.s. 100
Fragrance and ingredients q.s. for Formulation B
Diglycol/CHDM/Isophthalates/SIP copolymer 10 (Eastman AQ 55 S -
Eastman) Hydroxypropyl guar (Jaguar HP 105 - Rhodia) 2 Deionized
water q.s. 100 Fragrance and ingredients q.s. for
[0208] Eastman AQ 55 S, sold by Eastman, is a diethylene
glycol/1,4-cyclohexanedimethanol/isophthalate/sulphoisophthalate
copolymer.
Procedure:
[0209] 2 g of the formulation to be tested were applied to a lock
of natural hair weighing 2.7 g and with a length of 27 cm.
[0210] The treated lock was wound around a roller with a diameter
of 1 cm in order to give it a shape.
[0211] The combination was allowed to dry in the air and then the
lock was gently unwound from the roller.
[0212] The locks thus shaped were subsequently immersed in a salt
water bath (3% NaCl) with a volume of 8 liters at ambient
temperature with magnetic stirring at 100 revolutions/minute.
[0213] The length of the lock over time was measured in order to
evaluate the form retention of the hair shaping.
Measurements of the Form Retention of the Hair Shaping:
[0214] Form retention of the hair shaping in %:
(L.sub.i-L)/(L.sub.i-L.sub.0)*100
[0215] L: Length of the curled lock at time t
[0216] L.sub.0: Length of the curled lock after hair shaping and
removing from the roller
[0217] L.sub.i: Length of the lock before hair shaping on the
roller TABLE-US-00002 Form retention of the hair shaping in %
Immersion time A B 0 100 100 25 seconds 100 100 30 seconds 100 100
35 seconds 100 100 40 seconds 100 100 10 minutes 100 100
* * * * *